Zeolite beta and its use in aromatic alkylation

ABSTRACT

There is disclosed a new form of zeolite beta which shows substantially greater stability and greater catalyst lifetime when used in the alkylation and transalkylation of aromatic compounds. The new, surface-modified zeolite beta is characterized by having surface aluminum 2p binding energies as measured by X-ray photoelectron spectroscopy, of at least 74.8 electron volts. This surface-modified zeolite beta is prepared by treating a templated zeolite beta with an acid at a pH between about 0 and about 2 and a temperature up to about 125° C. for a time sufficient to modify the chemical environment of the surface aluminum atom without bringing about dealumination of the zeolite beta.

This application relates to a new form of zeolite beta and to its use asa catalyst in the alkylation of aromatics. More particularly, thisapplication relates to a zeolite beta which shows substantially greaterstability and catalyst life when used in the alkylation andtransalkylation of aromatics. It is contemplated that the catalysts ofthis invention may be particularly valuable in cumene production viaalkylation of benzene with propylene. For ease and simplicity ofexposition, the following description will make specific reference tothe use of our catalyst in the alkylation of benzene with propylene toafford cumene, but it is to be recognized that this is done solely forthe purpose of clarity and simplicity. We shall make frequent referenceto the broader scope of this application for emphasis.

Cumene is a major article of commerce, with one of its principal usesbeing a source of phenol and acetone via its air oxidation and asubsequent acid-catalyzed decomposition of the intermediatehydroperoxide, ##STR1## Because of the importance of both phenol andacetone as commodity chemicals, there has been much emphasis on thepreparation of cumene and the literature is replete with processes forits manufacture. Certainly the most common and perhaps the most directmethod of preparing cumene is the alkylation of benzene with propylene,especially using an acid catalyst. See "Encyclopedia of ChemicalProcessing and Design," J. J. McKetta and W. A. Cunningham, Editors, V.14, pp 33-51 (1982). Even though a high conversion of propylene and ahigh selectivity to monoalkylated products are two major prerequisitesof any commercially feasible process, other constraints must besatisfied.

The predominant orientation of the reaction of benzene with propylenecorresponds to Markownikoff addition resulting in cumene. However, asmall but very significant amount of the reaction occurs viaanti-Markownikoff addition to afford n-propylbenzene (NPB). Thesignificance of NPB formation is that it interferes with the oxidationof cumene to phenol and acetone, and consequently cumene used foroxidation must be quite pure with respect to NPB content. Since cumeneand NPB are difficult to separate by conventional means, as for exampledistillation, a constraint in the production of cumene by the alkylationof benzene is that the n-propylbenzene formed be minimized relative tocumene. An observation pertinent to this facet of alkylation is that therelative amount of NPB formation increases with increasing temperature.Thus, from the standpoint of minimizing NPB formation it is desirable toperform the alkylation at as low a temperature as possible. Stateddifferently, minimizing NPB requires avoiding high reactiontemperatures.

Turning to the catalysts used in aromatic alkylation, solid acidcatalysts are quite desirable from the viewpoint of designing acontinuous process. It is unnecessary to articulate here a litany ofsolid acid catalysts used in aromatic alkylation; suffice it to say thatmany are described and among these zeolitic catalysts have receivedspecial attention. Whatever catalyst is used, deactivation is a featurewhich can not be avoided but is to be minimized to the extent possible.For zeolitic catalysts deactivation usually results from theaccumulation of polyalkylated products on the catalyst surface andwithin the zeolite channels, and it has been observed that the rate ofdeactivation decreases with increasing reaction temperature. Thus,minimizing catalyst deactivation generally suggests performing thealkylation at relatively high reaction temperatures. Thus it is clearthat attempts to decrease catalyst deactivation by effecting reaction athigh temperatures is at variance with attempts to minimize NPB formationby effecting reaction at low temperatures.

What is required in an optimum catalyst for, e.g., cumene production, isa catalyst with sufficient activity to effect alkylation at acceptablereaction rates at temperatures sufficiently low to avoid unacceptableNPB formation while exhibiting the slow catalyst deactivation usuallyassociated with higher reaction temperatures. Because zeolite beta showssubstantially greater activity than other zeolites, it has receivedclose scrutiny as a catalyst in aromatic alkylation; see, e.g., Innes etal., U.S. Pat. No. 4,891,458, Shamshoum et al., U.S. Pat. No. 5,030,786,and EP 432,814 inter alia. However, it is found that zeolite betas asdescribed still deactivate at unacceptably high rates at the lowtemperatures desired to minimize NPB formation. In order for acommercial process based on zeolite beta to become a reality it is firstnecessary to either increase catalyst activity--i.e., increase the rateof cumene production at a given temperature--or to decrease catalystdeactivation--i.e., increase catalyst lifetime so as to increase cumeneproduction prior to catalyst regeneration. This application focuses onmaking modifications to native zeolite beta to afford a catalyst showingdecreased deactivation relative to other zeolite betas.

The rationale employed in our approach assumed catalyst deactivationresulted from polyalkylation of aromatics, perhaps with a minorcontribution from oligomerization, especially where the propyleneconcentration is quite large. We further assumed that polyalkylates (andother deactivating materials) formed mainly as a consequence of strongacid sites on the zeolite surface. We then concluded that formation ofdeactivating materials could be reduced by removing the stronger acidsites on the zeolite surface, especially by converting the strong acidsites to weaker ones ineffective, or less effective, in producingdeactivating materials. We have found that treating templated zeolitebeta with a low concentration of a strong mineral acid followed bycalcination affords a superior zeolite beta. The order of treatment iscritical; acid washing a calcined zeolite beta is largely ineffective|We believe that our treatment affects only the nature of surface acidsites, as shown by an unchanged silicon:aluminum surface ratio, and achanged surface aluminum 2p binding energy as determined by x-rayphotoelectron spectroscopy.

SUMMARY OF THE INVENTION

The purpose of our invention is to provide a modified zeolite betacatalyst active in the alkylation of aromatics with olefin and withdeactivation rates at a given temperature less than conventional zeolitebeta. An embodiment comprises a calcined, non-templated surface-modifiedzeolite beta having surface aluminum 2p binding energies, as measured byx-ray photoelectron spectroscopy, of at least 74.8 electron volts.Another embodiment comprises a method of making the aforesaidsurface-modified zeolite beta by treating the templated zeolite betawith nitric acid and ammonium nitrate at a pH of about 2 and at 70° C.for about 3 hours. In another aspect our invention is the alkylation ofaromatics by olefins catalyzed by a surface-modified zeolite beta asdescribed above. In a specific embodiment the olefin is propylene andthe aromatic hydrocarbon is benzene. In an additional embodiment theolefin is a detergent range olefin. In still another embodiment theolefin has from 8 to 16 carbon atoms. Other embodiments will becomeapparent from the ensuing description.

DESCRIPTION OF THE INVENTION

This invention is born of the necessity to catalyze the selectivemonoalkylation of benzene with propylene at as low a temperature aspossible while retaining the low deactivation rates manifested byzeolite beta as the catalyst at a substantially higher temperature. Onceborn the invention was seen to be applicable to the entire class ofaromatics alkylation by olefin. The key to our invention is surfacemodification of zeolite beta so as to decrease the surface acidityrequisite for polyalkylation, which is the major contributor to catalystdeactivation, and oligomerization, which is a minor contributor tocatalyst deactivation, while retaining the acid sites necessary tocatalyze the desired selective monoalkylation of aromatics. Ourinvention is applicable not only to the selective monoalkylation ofaromatics, but also to the transalkylation of polyalkylated aromatics.Thus it is readily seen that our invention is of unusually broad scope.

In the selective monoalkylation of aromatics by olefins as catalyzed bythe surface-modified zeolite beta of our invention the olefins maycontain from 2 up to at least 20 carbon atoms, and may be branched orlinear olefins, either terminal or internal olefins. Thus, the specificnature of the olefin is not particularly important. What the alkylationsshare in common is that the reactions are conducted under at leastpartially liquid phase conditions, a criterion readily achieved for thelower members by adjusting reaction pressures. Among the lower olefinsethylene and propylene are the most important representatives. Among theremaining olefins the class of detergent range olefins is of particularinterest. This class consists of linear olefins containing from 6 upthrough about 20 carbon atoms which have either internal or terminalunsaturation. Linear olefins containing from 8 to 16 carbon atoms areparticularly useful as detergent range olefins, and those containingfrom 10 up to about 14 carbon atoms are especially preferred.

Benzene is by far the most important representative of the alkylatablearomatic compounds which may be used in the practice of our invention.More generally the aromatic compounds may be selected from the groupconsisting of benzene, naphthalene, anthracene, phenanthrene, andsubstituted derivatives thereof. The most important class ofsubstituents found on the aromatic nucleus of alkylatable aromaticcompounds are alkyl moieties containing from 1 up to about 20 carbonatoms. Another important substituent is the hydroxyl moiety as well asthe alkoxy moiety whose alkyl group also contains from 1 up to 20 carbonatoms. Where the substituent is an alkyl or alkoxy group, a phenylmoiety also can be substituted on the paraffinic chain. Althoughunsubstituted and monosubstituted benzenes, naphthalenes, anthracenes,and phenanthrenes are most often used in the practice of this invention,polysubstituted aromatics also may be employed. Examples of suitablealkylatable aromatic compounds in addition to those cited above includebiphenyl, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene,pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, and so forth;phenol, cresol, anisole, ethoxy-, propoxy-, butoxy-, pentoxy-,hexoxybenzene, and so forth.

In that branch of our invention where our surface-modified zeolite betais used to catalyze selective monoalkylation of alkylatable aromaticcompounds, the particular conditions under which the reaction isconducted depends upon the aromatic compound and the olefin used. Sincethe reaction is conducted under at least partial liquid phaseconditions, reaction pressure is adjusted to maintain the olefin atleast partially dissolved in the liquid phase. For higher olefins thereaction may be conducted at autogenous pressure. As a practical matterthe pressure normally is in the range between about 200 and about 1,000psig (1379-6985 kPa) but usually is in a range between about 300-600psig (2069-4137 kPa). But we emphasize again that pressure is not acritical variable and needs to be sufficient only to maintain at leastpartial liquid phase conditions. Representative alkylation temperaturesinclude a range of between 200-250° C. for alkylation of benzene withethylene and temperatures of 90-200° C. for the alkylation of benzene bypropylene. The temperature range appropriate for alkylation of thealkylatable aromatic compounds of our invention with the olefins in theC2-C20 range is between about 60 and about 400° C., with the most usualtemperature range being between about 90 and 250° C.

The ratio of alkylatable aromatic compound to olefin used in the processwhich is our invention will depend upon the degree of selectivemonoalkylation desired as well as the relative costs of the aromatic andolefinic components of the reaction mixture. For alkylation of benzeneby propylene, benzene-to-olefin ratios may be as low as about 1 and ashigh as about 10, with a ratio of 2.5-8 being preferred. Where benzeneis alkylated with ethylene a benzene-to-olefin ratio between about 1:1and 8:1 is preferred. For detergent range olefins of C6-C20, abenzene-to-olefin ratio of between 5:1 up to as high as 30:1 isgenerally sufficient to ensure the desired monoalkylation selectivity,with a range between about 8:1 and about 20:1 even more highly desired.

As previously alluded to, the surface modified zeolite beta of ourinvention also can be used to catalyze transalkylation as well asalkylation. By "transalkylation" is meant that process where an alkylgroup on one aromatic nucleus is intermolecularly transferred to asecond aromatic nucleus. The transalkylation of particular interest hereis one where one or more alkyl groups of a polyalkylated aromaticcompound is transferred to a nonalkylated aromatic compound, and isexemplified by reaction of diisopropylbenzene with benzene to afford twomolecules of cumene. Thus, transalkylation often is utilized to add tothe selectivity of a desired selective monoalkylation by reacting thepolyalkylates invariably formed during alkylation with nonalkylatedaromatic to form additional monoalkylated products. For the purposes ofthis section the polyalkylated aromatic compounds are those formed inthe alkylation of alkylatable aromatic compounds with olefins asdescribed above, and the nonalkylated aromatic compounds are benzene,naphthalene, anthracene, and phenanathrene. The reaction conditions fortransalkylation are similar to those for alkylation, with temperaturesbeing in the range of 100 to about 250°, pressures in the range of 100to about 750 psig, and the molar ratio of unalkylated aromatic topolyalkylated aromatic being in the range from about 1 to about 10.Examples of polyalkylated aromatics which may be reacted with, e.g.,benzene as the nonalkylated aromatic include diethylbenzene,diisopropylbenzene, dibutylbenzene, triethylbenzene,triisopropylbenzene, and so forth.

The catalyst of our invention is a surface-modified zeolite beta whichresults from acid washing of a templated native zeolite beta. That is,the formation of the surface-modified zeolite beta starts with atemplated beta where the template is, for example, a tetraalkylammoniumsalt, such as a tetraethylammonium salt. It is critical to acid wash atemplated zeolite beta in order to protect the internal sites of thezeolite and to prevent dealumination. The templated zeolite beta istreated with a strong acid at a pH between about 0 up to about 2,although a pH under 1 is preferred. Acids which may be used includenitric acid, sulfuric acid, phosphoric acid, and so forth. For example,a weak, 0.01 molar nitric acid may be used in conjunction with ammoniumnitrate to perform the acid wash, although substantially higherconcentrations, up to about 20 weight percent nitric acid, arepreferred. Nitric acid is a preferred acid since it is a non-complexingacid and therefore does not encourage dealumination. Treatment of thetemplated zeolite beta with strong acid may be effected over thetemperature range between about 20° C. up to about 125° C. It isimportant that acid washing be done under conditions not so severe as toeffect dealumination.

The time over which acid washing is conducted is quite temperaturedependent. As mentioned previously, it is critical in the formation ofthe surface-modified zeolite beta of our invention that there be nosignificant bulk dealumination of the zeolite. Thus, as a generalstatement it can be said that acid washing should be done for a timeinsufficient to effect dealumination. For example, using 0.01 molarnitric acid and ca. 40% ammonium nitrate at 70° C., contact times of 2-3hours are found adequate to modify the environment of surface aluminumwithout causing significant bulk dealumination. Using ca. 15% nitricacid with ammonium nitrate to treat an ca. 25 weight percent slurry at85° C. a 90-minute treatment is effective. The dependent variables inacid washing include acid concentration, slurry concentration, time andtemperature, and suitable conditions at which surface-modified zeolitebeta can be prepared without significant bulk dealumination are readilydetermined by the skilled artisan.

Next the template is removed by calcination at temperatures in the rangeof 550°-700° C. Calcination conditions are well known in the art andneed not be elaborated upon here. It also needs to be mentioned thatpowdered zeolite itself is not usually used. Therefore, in the moreusual case after the templated zeolite beta is acid washed it is mixedwith a conventional binder, extruded, and the extrudate is ultimatelycalcined. But it is to be understood that the critical portion of ourpreparation is the acid wash of the templated beta according to theforegoing description. As will be seen within acid washing a calcined(i.e., non-templated) zeolite beta does not afford the surface-modifiedmaterial of our invention.

It has been found that after treatment as described above the surfacealuminum atoms are chemically modified. It is believed that themodification is in the form of replacement of strong acid sites at thecatalyst surface by weaker acids sites. However, it is to be clearlyunderstood that this is only a working hypothesis and that the successof our invention does not rest thereon. What has been definitelyobserved is that the surface aluminums of the modified zeolite beta ofour invention have 2p binding energies as measured by x-rayphotoelectron spectroscopy of at least 74.8 electron volts.

Alkylation of alkylatable compounds by the olefins of our invention maybe exemplified by the alkylation of benzene with propylene. Suchalkylation may be carried out in any of the ways which are well known tothose practicing the art. For example, the process in general can becarried out in a batch mode by heating the catalyst, aromatichydrocarbon, and olefin in a stirred autoclave at a temperature between60° and 400° C. and at sufficient pressure to maintain at least apartial liquid phase. The pressure typically will be in the range of 200to about 1000 psig, but serves only to ensure at least partial liquidphase reaction.

However, the process is more advantageously performed in the continuousmode employing a fixed bed reactor operating in an upflow or downflowmode or using a moving bed reactor operating with cocurrent orcountercurrent catalyst and hydrocarbon flows. The reactors also maycontain one or more catalyst beds and may be equipped for the interstageaddition of olefin as well as interstage cooling. Interstage olefinaddition ensures a more nearly isothermal operation and tends to enhanceproduct quality and catalyst life. A moving bed reactor provides theadvantage of continuous spent catalyst removal for regeneration andreplacement by fresh or regenerated catalyst. However, it also ispossible to carry out our invention using swing bed reactors.

Exemplifying the process of our invention by the alkylation of benzenewith propylene, the continuous alkylation may be performed using a fixedbed reactor. Benzene and propylene may be introduced into the reactor attemperatures between 90° and 160° C. The overall benzene-to-propyleneratio may be between 2 and about 10, although normally it is betweenabout 2.5 and about 8. Feedstock may be passed either upflow ordownflow, although a downflow mode is more conventional. Pressures of200-500 psig are generally employed with flow rates being in the regionof 1 to about 10 LHSV of benzene.

The following examples are only illustrative of our invention and do notlimit it in any way.

EXAMPLE 1

Preparation of acid washed zeolite betas.

Commercial zeolite beta, SiO₂ 92.2 wt. %, Al₂ O₃ 7.0 wt. %, LOI 24.3 wt.%, and N₂ BET 672 m2/g, identified as sample A in the followingexamples, was calcined in air at 650° C. for 2 hours. To a solution of1428 grams ammonium nitrate in 3224 grams distilled water was added 932grams of 70 weight percent nitric acid and the mixture was heated to 85°C. The calcined zeolite beta (1416 grams dry weight) was added and thismixture was stirred at 85° C. for 90 minutes. The slurry was filteredand washed using 10 liters of distilled water and then dried at 100° C.for 16 hours. Analysis showed a molar SiO₂ /Al₂ O₃ ratio of 137, SiO₂96.8 wt. %, Al₂ O₃ 1.2 wt. %, N₂ BET surface area 720 m2/g. This sampleis identified as sample B in the following examples.

Sample C was prepared essentially as described for sample B except that10% less nitric acid was used (839 grams 70% nitric acid). Analysesshowed SiO₂ 93.6 wt. %, Al₂ O₃ 1.5 wt. %, molar ratio SiO₂ /Al₂ O₃ 105,surface area 689 m2/g.

Samples D and E were prepared essentially as described for sample Bexcept that uncalcined zeolite beta powder was used as the raw material.The acid-treated material prior to calcination corresponds to sample D;material calcined after acid treatment (650° C. for 3 hours in air)corresponds to sample E. Analyses on E showed 91.7 wt. % SiO₂, 6.1 wt. %Al₂ O₃, molar ratio SiO₂ /Al₂ O₃ 25.5.

The samples were examined by x-ray photoelectron spectroscopy (XPS) todetermine binding energies as well as the surface silicon:aluminumatomic ratios. The results are summarized in Table 1.

                  TABLE 1                                                         ______________________________________                                                Binding Energies (eV)                                                 Peak    A         B       C       D     E                                     ______________________________________                                        Al2p    74.65     74.18   74.13   74.07 75.20                                 Si2p    103.30    103.30  103.30  103.30                                                                              103.30                                C 1s    284.48                    285.18                                      C 1s    286.80                    286.44                                      C 1s    288.80                                                                O 1s                              530.52                                      O 1s    532.53    532.44  532.45  532.47                                                                              532.43                                Surface Concentrations (atomic %)                                             Al      1.83      0.41    0.35    1.44  1.93                                  Si      26.66     30.99   31.88   24.28 29.91                                 Si/Al (bulk)                                                                          ≈15                                                                             ≈68                                                                           ≈53                                                                           ≈15                                                                         ≈13                           Si/Al (XPS)                                                                           15        76      91      17    16                                    ______________________________________                                    

The binding energies of Si2p and O1s are typical for highly siliceouszeolites. It is noteworthy that the Al2p binding energy for thereference sample A is about 0.5 eV higher than for all acid washedsamples. This indicates that the aluminum in the precursor sample ismost likely in the framework. The Al2p binding energy of about 74.1 eVfor all acid washed samples is more typical of free alumina. It also isnoteworthy that for the acid washed and calcined sample E the Al2pbinding energy is about 0.5 eV higher than for the reference sample. Italso is seen that the surface and bulk Si/Al ratios are about the samewithin the uncertainties associated with measurements of very low Alconcentrations.

These data strongly indicate that the surface aluminum concentration hasnot been reduced relative to the bulk aluminum concentration (i.e.,there has been no surface dealumination) and also indicates that thenature of aluminum on the surface has been altered.

EXAMPLE 2

Alkylation of benzene with propylene using various zeolite betas.

In all cases the samples described above which were used in reactortesting were bound with alumina (70/30 zeolite/binder), extruded (1/16"extrudates), dried, then calcined at 650° C. for 2 hours. For each test10 cc of 1/16" extrudates were loaded into a reactor to form a bed 1/2"in diameter and 33/4" to 4" long. The catalyst was activated for 12hours by passing a stream of benzene over the catalyst at 140° C., 500psig and 6 benzene LHSV. Temperature was adjusted to the desired runtemperature and the feed switched to a blend of 6 weight percentpropylene in benzene at 6 LHSV. The position of the maximum temperature(due to the exothermic reaction) in the bed was noted. Deactivation wasdetermined by noting the position of the maximum temperature after 48hours at test conditions. Deactivation is calculated by taking thedifference in these two positions (in inches), dividing by the bedlength (in inches) and then dividing by the time interval (in days). Theresults are multiplied by 100% to give a deactivation rate in percent ofcatalyst bed/day.

Two catalyst samples (I, II) prepared by first calcining the zeolitebeta as a powder followed by acid washing, were tested at 130° C. SampleI and II are analogous to samples B and C of the prior example. Bothcatalysts exhibited propylene breakthrough before the end of the 48 hourtest period, resulting in 100% deactivation or >50%/day. The catalyst ofthe invention, III, analogous to sample E of the prior example, wastested at 130° with the results shown in the table.

    ______________________________________                                        Catalyst    Deactivation (%/day)                                              ______________________________________                                        I           >50                                                               II          >50                                                               III         10.3                                                              ______________________________________                                    

These results, obtained under experimental conditions as identical aspossible save for the catalyst, unequivocally demonstrate the vastsuperiority of our catalysts.

What is claimed is:
 1. A process for preparing cumene by the alkylationof benzene with propylene comprising reacting propylene with from 2 upto about 10 molar proportions of benzene at a temperature between about90° and about 200° C. at a pressure sufficient to maintain at least apartial liquid phase in the presence of a calcined, non-templated,surface-modified zeolite beta whose surface aluminum atoms have a 2pbinding energy of at least 74.8 electron volts as determined by X-rayphotoelectron spectroscopy.
 2. The process of claim 1 where propylene isreacted with from 2.5 up to about 8 molar proportions of benzene.
 3. Theprocess of claim 1 where the reaction temperature is from about 90° upto about 160° C.
 4. The process of claim 1 where the pressure is fromabout 200 up to about 1000 psig.
 5. The process of claim 4 where thepressure is from about 200 up to about 500 psig.
 6. A method ofmonoalkylating aromatics comprising reacting under alkylation conditionsand under at least partial liquid phase conditions an olefin with from 1up to about 30 molar proportions of an alkylatable aromatic compound inthe presence of a calcined, non-templated, surface-modified zeolite betawhose surface aluminum atoms have a 2p binding energy of at least 74.8electron volts as determined by X-ray photoelectron spectroscopy.
 7. Themethod of claim 6 where the olefin contains from 2 up to about 20 carbonatoms.
 8. The method of claim 7 where the olefin contains from 6 up toabout 20 carbon atoms.
 9. The method of claim 8 where the olefincontains from about 8 up to about 16 carbon atoms.
 10. The method ofclaim 9 where the olefin contains from about 10 up to about 14 carbonatoms.
 11. The method of claim 6 where the alkylatable aromatic compoundis selected from the group consisting of benzene, naphthalene,anthracene, phenanthrene, and substituted derivatives thereof.
 12. Themethod of claim 6 where the alkylatable aromatic compound is benzene.13. The method of claim 6 where the alkylatable aromatic compound is analkyl-, hydroxyl-, or alkoxy-substituted benzene, naphthalene,anthracene, or phenanthrene, where the alkyl or alkoxy group containsfrom 1 up to about 20 carbon atoms.
 14. The method of claim 6 wherereaction conditions include a temperature from about 60° up to about400° C. and a reaction pressure up to about 1000 psig.
 15. Atransalkylation process comprising reacting under transalkylationreaction conditions a polyalkylated aromatic compound with anonalkylated aromatic compound in the presence of zeolite beta, whereinat least one alkyl group is transferred from the polyalkylated aromaticcompound to the nonalkylated aromatic compound, where said zeolite betais a calcined, non-templated, surface-modified zeolite beta whosesurface aluminum atoms have a 2p binding energy of at least 74.8electron volts as determined by X-ray photoelectron spectroscopy. 16.The process of claim 15 where the alkyl groups of the polyalkylatedaromatic compound contain from about 2 up to about 20 carbon atoms. 17.The process of claim 16 where the alkyl groups contain from 6 up toabout 20 carbon atoms.
 18. The process of claim 16 where the alkylgroups contain from 8 up to about 16 carbon atoms.
 19. The process ofclaim 16 where the nonalkylated aromatic compound is selected from thegroup consisting of benzene, naphthalene, anthracene, phenanthrene, andsubstituted derivatives thereof.
 20. The process of claim 16 where saidpolyalkylated aromatic compound is a polyisopropyl benzene and thenonalkylated compound is benzene.